Kinetics and thermodynamic behavior of WO3 and WO3:P thin films

 There is a considerable interest in the research and development of materials and devices, that can be used for optical switching of large-scale glazings. Several potential switching technologies are available for glazings, including those based on electrochromic, thermochromic and photochromic phenomena. One of the most promising technologies for optical switching devices is electrochromism (EC). In order to improve the electrochromic properties of tungsten oxide, we have investigated the effect of phosphorous insertion on the electrochromic behavior of oxide films prepared by the sol–gel process.The kinetics and thermodynamics of electrochemical intercalation of lithium into Li_xWO₃ and Li_xWO₃:P films prepared by the sol–gel process were investigated. The standard Gibbs energy for lithium intercalation was calculated. The chemical diffusion coefficients, D, of lithium intercalation into oxide, were measured by galvanostatic intermittent titration technique (GITT), as functions of the depth of lithium intercalation.     

Electrochromic interference filters fabricated from dense and porous tungsten oxide films

Smart windows offer an opportunity to reduce energy consumption. However, the use of multiple optical elements, such as low emittance coatings and electrochromic devices, is detrimental to the luminous transmittance of these high performance windows. Although the addition of antireflective coatings has helped to reduce this problem, some elements, such as high index of refraction materials still give rise to loss of light. We show that replacing the single WO₃ active coating, the main component of an electrochromic device, by an appropriately designed electrochromic interference filter can significantly increase the transmittance. This active filter is based on a stack of dense and porous WO₃ layers. We first study the effect of porosity on the physical and electrochromic properties of WO₃ prepared by radio frequency magnetron sputtering. We demonstrate that the overlying dense coating does not inhibit the coloration of the underlying porous coating. The best performing films are combined into a 27 layer quarter-wave interference filter which is shown to cycle between bleached and colored states, while providing attractive transmission. Finally, we discuss various filter designs which can increase the transmission of an electrochromic device in its bleached state, as well as the potential use of active filters for optical security devices possessing two levels of authentication.     

Step potential analysis of cobalt oxide-based electrochromic devices

The characterization of electrochemical behavior of electrochromic intercalation device based on cobalt oxide thin film was carried out using the step potential excitation method. A method based on generating plots of current density as a function of passed charge has been applied for characterization of electrochromic cobalt oxide thin films using an aqueous KOH electrolyte. The device resistance and the intercalation capacity of the material are calculated. Dynamic built-in potential estimated from step potential experiment and plots of the built-in potential as function of the passed charge, V_bi(ΔQ), are generated for intercalation process. The intercalation efficiency curve is obtained to confirm the nature of energy distribution of intercalation sites in electrochromic cobalt oxide.     

Transparent conductors as solar energy materials: A panoramic review

Transparent conductors (TCs) have a multitude of applications for solar energy utilization and for energy savings, especially in buildings. The largest of these applications, in terms of area, make use of the fact that the TCs have low infrared emittance and hence can be used to improve the thermal properties of modern fenestration. Depending on whether the TCs are reflecting or not in the near infrared pertinent to solar irradiation, the TCs can serve in “solar control” or “low-emittance” windows. Other applications rely on the electrical conductivity of the TCs, which make them useful as current collectors in solar cells and for inserting and extracting electrical charge in electrochromic “smart windows” capable of combining energy efficiency and indoor comfort in buildings. This Review takes a “panoramic” view on TCs and discusses their properties from the perspective of the radiative properties in our ambience. This approach leads naturally to considerations of spectral selectivity, angular selectivity, and temporal variability of TCs, as covered in three subsequent sections. The spectrally selective materials are thin films based on metals (normally gold or titanium nitride) or wide band gap semiconductors with heavy doping (normally based on indium, tin, or zinc). Their applications to energy-efficient windows are covered in detail, experimentally as well as theoretically, and briefer discussions are given applications to solar cells and solar collectors. Photocatalytic properties and super-hydrophilicity are touched upon. Angular selective TCs, for which the angular properties are caused by inclined columnar nanostructures, are then covered. A discussion of TC-like materials with thermochromic and electrochromic properties follows in the final part. Detailed treatments are given for thermochromic materials based on vanadium dioxide and for electrochromic multi-layer structures (incorporating TCs as essential components). The reference list is extensive and aims at giving an easy entrance to the many varied aspects of TCs.     

A complementary electrochromic device based on polyaniline-tethered polyhedral oligomeric silsesquioxane and tungsten oxide

In this paper we report a high-contrast complementary electrochromic device based on polyaniline-tethered polyhedral oligomeric silsesquioxane (POSS-PANI) and tungsten oxide (WO₃). The electrochromic properties, cyclic voltammetry behavior and coloration efficiency of the device are studied. Due to the loosely packed structure of POSS-PANI, it possesses more accessible doping sites and hence gives rise to a significantly higher electrochromic contrast than polyaniline (PANI). Furthermore, the replacement of PANI with POSS-PANI as the complementary layer for WO₃ leads to an enhanced complementary effect, for which the underneath mechanism is also discussed.     

Application issues for large-area electrochromic windows in commercial buildings

Projections of performance from small-area devices to large-area windows and enterprise marketing have created high expectations for electrochromic glazings. As a result, this paper seeks to precipitate an objective dialog between material scientists and building-application scientists to determine whether actual large-area electrochromic devices will result in significant performance benefits and what material improvements are needed, if any, to make electrochromics more practical for commercial building applications.Few in situ tests have been conducted with large-area electrochromic windows applied in buildings. This study presents monitored results from a full-scale field test of large-area electrochromic windows to illustrate how this technology will perform in commercial buildings. The visible transmittance (T_v) of the installed electrochromic ranged from 0.11 to 0.38. The data are limited to the winter period for a south-east-facing window. The effect of actual device performance on lighting energy use, direct sun control, discomfort glare, and interior illumination is discussed. No mechanical system loads were monitored. These data demonstrate the use of electrochromics in a moderate climate and focus on the most restrictive visual task: computer use in offices.Through this small demonstration, we were able to determine that electrochromic windows can indeed provide unmitigated transparent views and a level of dynamic illumination control never before seen in architectural glazing materials. Daily lighting energy use was 6–24% less compared to the 11%-glazing, with improved interior brightness levels. Daily lighting energy use was 3% less to 13% more compared to the 38%-glazing, with improved window brightness control. The electrochromic window may not be able to fulfill both energy-efficiency and visual comfort objectives when low winter direct sun is present, particularly for computer tasks using cathode-ray tube (CRT) displays. However, window and architectural design as well as electrochromic control options are suggested as methods to broaden the applicability of electrochromics for commercial buildings. Without further modification, its applicability is expected to be limited during cold winter periods due to its slow switching speed.     

d-Electrons and two active thin film devices for achieving a solar energy economy

In this paper, the marriage of condensed matter science and solar energy technologies will be illustrated by two closely related active thin film devices, a variable reflectivity electrochromic window and a high energy density rechargeable (or secondary) thin film battery. Each device can significantly assist in achieving a solar energy economy. The primary focus of this paper is the important role of d-electrons in two candidate thin film materials, tungsten oxide and lithium cobalt oxide, that could be utilized in one or in both the devices, respectively.     

Electrochromic characterization of sol–gel deposited coatings

Electrochromic devices have increasing application in large-area display devices, switchable mirrors and smart windows. A variety of vacuum deposition technologies have been used to make electrochromic devices. The sol–gel process offers an alternative approach to the synthesis of low-cost, high-quality electrochromic device layers. This paper discusses the developments in sol–gel-deposited electrochromic films and a prototype all sol–gel device with switching from 80% to 50% (550 nm). The sol–gel process involves the formation of oxide networks upon hydrolysis–condensation of alkoxide precursors. In this study, we cover sol–gel-deposited oxides of WO₃, TiO₂, Nb₂O₅, V₂O₅, Ni(OH)₂, Co(OH)₂ and CuO_x. The coloration reaction voltammetry and spectral optical properties are presented for selected films.     

Electrochromic behavior of Ni---W oxide electrodes

A new electrochromic material, Ni---W oxide, was fabricated by a reactive sputtering method and the effects of tungsten concentration in Ni---W oxide thin films on the electrochromic behavior were investigated. It has been found that the charge transfer resistance which has been known to be very high in NiO_x becomes significantly low with the addition of tungsten in NiO_x. It turned out that the charge transfer density during the cyclic voltammetry increased considerably with the addition of tungsten in NiO_x such that at an optimum concentration of tungsten (atomic ratio of W/Ni = 0.33), a fast optical switching with the insertion and removal of lithium in Ni---W oxide thin films could be expected. The electrochromic display device composed K_0.3WO_3.15 and Ni---W oxide was fabricated and its optical switching characterized.     

Electrochromic properties of nanocomposite WO3 films

A new nanocomposite WO₃ (NWO) film-based electrochromic layer was fabricated by a spray and electroplating technique in sequence. An indium–tin oxide (ITO) nanoparticle layer was employed as a permanent template to generate the particular nanostructure. The structure and morphology of the NWO film were characterized. The optical and electrochromic properties of the NWO films under lithium intercalation are described and compared to the regular WO₃ film. The NWO films showed an improved cycling life and an improved contrast with compatible bleach-coloration transition time, owing to the larger reactive surface area. The nanocomposite WO₃ film-based electrochromic device (NWO-ECD) was also successfully fabricated. Most importantly, the NWO film can be prepared on a large scale directly onto a transparent conductive substrate, which demonstrates its potential for many electrochromic applications, especially, smart windows, sunroof and displays.     

A comparison of absorptance and reflectance modulation variable transmission electrochromic devices

A comparison is made of the optical properties and electrochromic performance of two types of electrochromic device for use as variable transmission glazing. The devices employ respectively amorphous tungsten oxide and crystalline tungsten oxide as the active electrochromic layer. Both devices exhibit pronounced transmission modulation. Some measure of reflectance modulation is observable for the crystalline tungsten oxide device.     

Electrochromic tungsten oxide films: Review of progress 1993–1998

W oxide films are of critical importance for electrochromic device technology, such as for smart windows capable of varying the throughput of visible light and solar energy. This paper reviews the progress that has taken place since 1993 with regard to film deposition, characterization by physical and chemical techniques, optical properties, as well as electrochromic device assembly and performance. The main goal is to provide an easy entrance to the relevant scientific literature.     

Recent advances in electrochromics for smart windows applications

Electrochromic smart windows are able to vary their throughput of radiant energy by low-voltage electrical pulses. This function is caused by reversible shuttling of electrons and charge balancing ions between an electrochromic thin film and a transparent counter electrode. The ion transport takes place via a solid electrolyte. Charge transport is evoked by a voltage applied between transparent electrical conductors surrounding the electrochromic film/electrolyte/counter electrode stack. This review summarizes recent progress concerning: (i) calculated optical properties of crystalline WO₃, (ii) electrochromic properties of heavily disordered W oxide and oxyfluoride films produced by reactive magnetron bias sputtering, (iii) novel transparent reactively sputter-deposited Zr–Ce oxide counter electrodes and (iv) a new proton-conducting antimonic-acid-based polymer electrolyte. Special in depth presentations are given on elastic light scattering from W-oxide-based films and of electronic band structure effects affecting opto–chronopotentiometry data in Zr–Ce oxide. The review also contains some new device data for an electrochromic smart window capable of very high optical transmittance.     

V0.50Ti0.50Ox thin films as counterelectrodes for electrochromic devices

Thin films of V_0.50Ti_0.50O_x have been deposited by RF sputtering from metallic targets. Their use as potential counterelectrodes in electrochromic devices has been investigated. It is found that although they are slightly yellow looking in transmission, the films can reversibly store relatively large amounts of charge, whilst showing a reasonably low electrochromic colouration efficiency. The electrochemistry of V_0.50Ti_0.50O_x is found to be simple, in fact rather similar to that of WO₃, making it an almost ideal material to use in such a variable transmission device.     

Intercalation studies on electron beam evaporated MoO3 films for electrochemical devices

Now-a-days a large number of extensive research has been focused on electrochromic oxide thin films, owing to their potential applications in smart windows, low cost materials in filters, low cost electrochemical devices and also in solar cell windows. Among the varieties of electrochromic transition metal oxides, the molybdenum oxide (MoO₃) and tungsten oxide (WO₃), form a group of predominant ionic solids that exhibit electrochromic effect. The electrochromic response of these materials are aesthetically superior to many other electrochromic materials, because WO₃ and MoO₃ absorb light more intensely and uniformly. In the present case, we have discussed about the electrochromic behaviour of electron beam evaporated MoO₃ films. Moreover, the MoO₃ film can also be used as a potential electro-active material for high energy density secondary lithium ion batteries; because it exhibits two-dimensional van der Waals bonded layered structure in orthorhombic phase. The films were prepared by evaporating the palletized MoO₃ powder under the vacuum of the order of 1 × 10⁻⁵ mbar. The electrochemical behaviour of the films was studied by intercalating/deintercalating the K⁺ ions from KCl electrolyte solutions using three electrode electrochemical cell by the cyclic-voltammetry technique. The studies were carried out for different scanning rates. The films have changed their colour as dark blue in the colouration process and returns to the original colour while the bleaching process. The diffusion coefficient values (D) of the intercalated/deintercalated films were calculated by Randle's Servcik equation. The optical transparency of the coloured and bleached films was studied by the UV–Vis–NIR spectrophotometer. The change in bonding assignment of the intercalated MoO₃ films was studied by FTIR spectroscopic analysis. A feasible study on the effect of substrate temperatures and annealing temperatures on optical density (OD) and colouration efficiency of the films were discussed and explored their performance for the low cost electrochemical devices.     

Development and testing of thermochromic coatings for buildings and urban structures

The present study reports the development and comparative testing of thermochromic coating to be used in buildings and urban structures. Experimental results from an extensive comparative analysis of the thermal and physical behaviour of thermochromic, highly reflective (cool), and common coatings are reported and analyzed. The surface temperature was monitored on 24 h basis from August to mid-September 2007. It was revealing that the temperature of thermochromic coatings was lower than cool and common coatings. Measurements of spectral reflectance indicated that the thermochromic coatings at the colored phase (below the transition temperature of 30 °C) are energy-absorbing while at the colorless phase (above the transition temperature of 30 °C) are energy-reflecting. The data obtained was used for the calculation of solar reflectance. The results showed that the solar reflectance of the thermochromic samples was significally higher compared to the cool and common ones. A 10-day period test was also performed showing the impact of solar radiation on thermochromism.The comparative results demonstrate that the use of thermochromic coatings can both contribute to energy savings in buildings, providing a thermally comfortable indoor environment, while can contribute highly to improve the urban microclimate.     

Energy,economic and environmental benefits of using high-efficiency motors to replace standard motors for the Malaysian industries

Electric motors use major share (i.e. about 30–80% of total industrial energy consumption) of total industrial energy use around the world. Experiences from other countries show that government intervention in the form of regulations such as mandatory and voluntary approaches can save sizeable amount of energy along with the reduction in emissions associated with energy savings. This paper presents potential energy savings by introducing high-efficiency motors as a case study in Malaysian industrial sector. Emission reductions associated with the energy savings has been estimated and presented as well. It was also estimated that a cumulative amount of 1940 and 892 GWh of energy can be saved for 20 and 120 kW motors, respectively, in Malaysia relative to BAU over the next 10 years. Similarly, a cumulative amount of USD 100 million and USD 60 million can be saved as utility bills for the same motor categories. It has been found that the payback period of different capacities of motors are less than a year. Based on results, it was found that 1789 million kg of CO₂ emission can be avoided by replacing standard motors with high-efficiency motors.     

Environmental assessment of electrochromic glazing production

The life cycle analysis method was used to determine the environmental impacts associated with the production of an electrochromic (EC) glazing (called ECD). This paper describes the inventory analysis for all the basic materials used during the manufacture of the ECD, i.e. K-Glass, tungsten oxide (WO₃), poly-methyl methacrylate (PMMA), propylene carbonate (PC), lithium perchlorate (LiClO₄) and acetic silicone sealant. K-Glass, PC and PMMA account for the 98% of the total device mass and the CO₂ emissions during their production processes are 810 g. The total embodied energy was estimated to be 49 MJ/ECD, with 32.1 MJ/unit of them derived from the K-Glass. The comparison of the total embodied energies of the ECD and various insulating glass units concluded that mass-produced EC glazings could easily compete with them in terms of environmental performance, anticipating cost attenuation and overall thermal and optical behavior. The above analysis could be implemented for the reduction of the embodied energy of the ECD life cycle, since it is proposed as an energy saving device.     

An all-solid-state electrochromic device based on NiO/WO3 complementary structure and solid hybrid polyelectrolyte

An all-solid-state electrochromic (EC) device based on NiO/WO₃ complementary structure and solid polyelectrolyte was manufactured for modulating the optical transmittance. The device consists of WO₃ film as the main electrochromic layer, single-phase hybrid polyelectrolyte as the Li⁺ ion conductor layer, and NiO film as the counter electrochromic layer. Indium tin oxide- (ITO) coated glass was used as substrate and ITO films act as the transparent conductive electrodes. The effective area of the device is 5×5 cm². The device showed an optical modulation of 55% at 550 nm and achieved a coloration efficiency of 87 cm² C⁻¹. The response time of the device is found to be about 10 s for coloring step and 20 s for bleaching step. The electrochromic mechanism in the NiO/WO₃ complementary structure with Li⁺ ion insertion and extraction was investigated by means of cyclic voltammograms (CV) and X-ray photoelectron spectroscopy (XPS).